Process for reforming gases



Feb. 26, 1935.

G. A. DAVIS PROCESS FOR REFORMING GASES Filed Dec. 23, 1931 2Shets-Sheec 1 E=El -INVENTOR Mam BY ATTORNEY Feb. 26, 1935. G, DAV|$1,992,909

PROCESS FOR REFORMING GASES Filed Dec. 23, 1931 2 Sheets-Sheet 2 Hydracarun 627565 INVENTOR I a M 'J' ATTORNEY Patented Feb. 26, 1935 UNITEDSTATES PATENT OFFICE PROCESS FOR REFORMING GASES George Alan Davis,Irvlngton, N. 1., assignor to Victor N. Roadstrum, West Orange, N. 1.

Application December 28, 1931, Serial No. 583,502

10 Claim.

5 either separately in a substantially pure state,

or in various mixtures thereof,--into reformed fixed combustible gasessuitable for use in standard or existing domestic burners withoutrequiring any changes in the burners or adjustment thereof, whichreformed gases are interchangeable as to use in said burners with thepresent day standard city gases manufactured for domestic use.

Typical manufactured city gases are: retort coal gas and carburettedwater gas. Such manue factured gases and also various essentiallyhydrocarbon gases have all found widespread use in domestic andindustrial application. However, when the essential hydrocarbon gasesare appliedin their natural or original state---in domestic burningappliances it is well known that they are not interchangeable with saidmanufactured city gas because of the different char-. acteristics orproperties thereof. While all of these gases have had a fairlywidespread use, nevertheless, the cost of transportation heretoforeconfined the use of certain essential hydrocarbon gases to localizedareas.

Refinements recently adopted in the petroleum industry have made thevarious hydrocarbon gases available in large quantities; and also recentimprovements in transportation facilities have permitted the widespreaddistribution of such gases.

However, the widespread'utilization of these hydrocarbon gases in thegas industry has heretofore been limited by their dissimilar propertiesas compared with standard manufactured city gases. Dissimilar gases arenot mutually interchangeable on standard gas appliances withoutcorresponding changes in design and adjustment of such appliances. Anygas appliance is designed and adjusted for the specific gas to be used.The chief properties of gas which influ ence the appliance design are:

(a) Heating value.

(b) Specific gravity.

() Rate of flame propagation.

The tolerance range for any of the above mentioned properties islimited. As a general proposition for efiicient operation of anappliance, the heating value of a gas should not deviate more than tofrom that which the appliance is designed for; the specific gravityshould deviate not more than 10-20% and rate of flame propagation shouldbe as nearly constant as possible.

Acomparison of the properties of the several hydrocarbon gases andstandard manufactured gas is as follows:--

ggg g Specific Rate of flame II/cu. i gravity propagation Typical std.mfg. city gas. 530- 550 50- .65 High Typical natural gas 1000-1200 60-70 Low Oil cracking still gas 1200-2000 80-1. 10 Medium tolow Propane2500 1. 52 Low Butane 3200 2. 00 Low tion herein described are asfollows:

(1) To convert or reform hydrocarbon gases to meet predeterminedspecifications relative to (a) heating value, (b) specific gravity, and(0) rate of flame propagation, so that the reformed gas is suitable fordistribution in manufactured city gas systems without altering thedesign or adjustment of appliances.

(2) To utilize economically, the hydrocarbon gases, from natural gasfields and oil cracking plants, which are so frequently wasted.

(3) To provide a' flexible process and means of producing a reformed gasto meet standard city gas specifications, from gaseous hydrocarbons bycompletely converting same at high thermal efficiency and withoutformation of liquid products or carbon residue.

(4) To provide a process for converting gaseous hydrocarbons to meetstandard city gas requirements without the use of solid fuel such ascoke or coal.

(5) To provide a simple means whereby the reforming of hydrocarbon gasesaccording to my new process is enabled to be carried out in existingmanufactured city gas equipment.

For the purpose of this invention the expression hydrocarbon gases, orthe expression essentially hydrocarbon gases is to be construed ascovering a single natural gas, such as methane, ethane, propane, butane,or oil cracking still gas, or any gaseous substance or composition whichincludes in the main any one, two, or more of these gases.

According to one manner of realizing the invention the invention iscarried out in a cycle the operation of which comprehends thecombination of three distinct steps consecutively carried out namely asfollows-assuming the gas reforming apparatus is in normal operationa-(1) The decomposition step wherein hydrocar-' bon gases are decomposedor reacted upon into gases of lighter specific gravity accompanied by adeposition of free carbon-during this step there is a consequent coolingof the reforming chamber to the minimum temperature for the cycle.

(2) The air blowing step wherein some but not all of the depositedcarbon is converted,--due to partial combustion, into producergas-during this stage there is a consequent heating of the reformingchamber to the maximum temperature for the cycle.

(3) The steam injection step wherein the remaining carbon and introducedsteam react to produce water gas-during this step there is a consequentcooling of the reforming chamber to an intermediate temperature for thecycle.

DECOMPOSITION STEP Step 1.In this step the hydrocarbon gases are passedinto the gas reforming chamber (pre-. viously heated to the requiredtemperature) wherein they are partially decomposed or reacted upon inthe presence of catalyst preferably containing nickel. The extent of thedecomposition depends upon the temperature, the rate of thruput and thecharacter of the catalyst. The products of decomposition are (1) a gas,composed largely of hydrogen, methane, and undecomposed hydrocarbon,which passes out of the reformer and is subsequently recovered; and (2)free carbon, substantially all of which is retained on the surface ofthe catalyst. This reaction is endothermic, causing the reformertemperature to drop 50-300 F. below the initial temperature of thisstep.

Am BLOWING STEP Step 2.-In this step the reformer is purged with air toserve two purposes: first, part of the carbon deposited on the catalystduring Step 1 is converted to producer gas; and second, as a consequenceof the exothermic nature of the reaction the temperature of the reformeris raised 50-600 F. above the initial temperature of this step. Theproducer gas formed passes out of the reformer and as desired part orall is subsequently recovered.

STEAM INJECTION STEP Step 3.-In this step steam is passed into thereformer, where it breaks up and combines or reacts with the balance ofthe carbon present to produce water gas. This reaction is endothermic,causing the reformer temperature to drop 50-300 F. below the initialtemperature of this step. The water gas produced passes out of thereformer, and is subsequently recovered.

The three steps above described constitute a complete cycle; and thecycles are repeated.

All of the gases produced and recovered during the decomposition stageare mixed with all or part of the gases produced and recovered duringthe air blowing step and also with all or part of the gases produced andrecovered during the steam injection step; the resulting mixtureconstituting the "reformed gases.

The initial temperature of the cycle, and the rate of thruput andduration of the respective stages are determined by the specificationsof the reformed gas desired. As an example of the application of myprocess for the manufacture of a reformed gas having a heating value of550 B. t. u. per cu. ft. and a specific gravity of .62 from a commercialbutane I cite the following cycle schedule: a

Per. cu. ft. of 550 B. t. u. reformed gas:-

Step 1 Cu. it. of gas made 548 Awmga Analysisz-GnHm 3.0%

H: 68.0 Max. temp. 1300 F Cnlm 29.0 1115 R Eagiifffffififi: .4%

Step 2 Cu. it. of gas made 920 Analysis-C01 14.0% Max. temp. 1450" I.inw p- 111 F g f l fffffffg gg 3.

Step 3 Cu. it. of gas made 242 Analysisz-CO; 1a 0% H1 56.0 Max. temp. 50F 00 32.0 CH4 Trace. Min. t p 1300" F 3 Of the .920 cu. ft. of gasrecovered during Step 2, .210 cu. ft. is used in the mixed gas, and thebalance purged to the atmosphere, or utilized in waste heat boilers.

Hmr BALANCE The invention, however, according to certain aspectsthereof, is not limited to the above cycle described, wherein the threesteps are carried out separately. It is also possible to producereformed gases of various compositions by employing other schedules ofoperation as follows:-

(1) Any two of the steps may be jointly carried out, e. g. air andhydrocarbon gas may be passed into the reformer simultaneously, thuscombining steps (1) and (2) (2) With the nickel catalyst all three stepsmay be simultaneously carried out and certain advantageous resultsrealized.

(3) Any one of the three steps may be jointly carried out, with part ofany other step, e. g. part of the volume of air used may be passed intothe reformer with the hydrocarbon gas, the balance of the volume of airrequired being passed in separately.

(4) Any two of the steps may be jointly carried out with part of thethird step, e. g. the steam, hydrocarbon. gas, and part of the volume ofair used may be passed into the generator at the same time, the balanceof the air being passed in separately.

As illustrative of certain manners in which the invention may berealized and employed reference is made to the drawings forming part ofthis specification and in which drawings;

Figure 1 is an elevation partly in vertical section showing the generalarrangement of the gas reformer. The gas reformer as shown in saidFigure 1 is an apparatus having suitable piping connections and a gasreforming or reacting chamber filled with a catalytic substance,preferably pure nickel wire in the form of helical springs.

Figure 2 is a diagram of a system employing the reformer of Figure 1 butaccording to the arrangement of Figure 2 the gases produced, as fromeach step of the reformer, are passed into a storage holder and thereinblended.

Figure 3 is a diagram of a system employing the reformer of Figure 1 butaccording to the arrangement of Figure 3 the gases produced in thereformer, as during operating Steps 1 and 3 of the reformer, are passedinto a storageholder; and the gases produced as during operating Step 2of the reformer, are passed to a lean gas relief holder, and therefromby means of a B. t. u. controller to the storage holder in the properquantity to maintain constant the heating value of the mixed gases inthe storage holder.

Figure 4 is a diagram of a system employing the reformer of Figure 1 butaccording to the arrangement of. Figure 4 a system, such as shown inFigure 3, has been adapted to an existing manufactured gas plant wherebythe reformed gases produced as from Steps 1 and 3 of the reformer arecaused to pass into the general storage holder with the existingmanufactured gas, and whereby the gases produced as from Step 2 of thereformer are caused to pass into the lean gas holder and therefrom bymeans of a B. t. u. controller into the storage holder wherein the gasesfrom the lean gas holder are admixed in predetermined proportions withthe gases in the storage holder to maintain a constant B. t. u. of suchmixed gases.

It will be here noted that Figures 2, 3 and 4 illustratediagrammatically how the gas reformer of Figure 1 and the reformed gasestherefrom can be commercially employed. Therefore, the construction ofthe gas reformer of Figures 1-4 inclusive, mode of operation, theprocess carried out therein and the type of product produced thereby andtherein will be described fully in detail before further reference ismade to the arrangement and functioning of the system or plant ofFigures 2, 3 and 4. Reference will now be made to the drawings indetail.

GAS REFORMERFIGURE 1 The gas reformer or gas reforming apparatus, as agas reforming system as a whole may be referred to, is herein designatedby R. It includes the gas reforming or reacting chamber 1 which isprovided with a refractory lining 2 surrounded with heat insulatingmaterial as 3.

The gas reforming chamber is provided with a bars, etc., or nickel cladsteel, or refractory material impregnated with reduced nickel (accordingto any of the several methods well known to the art). The catalyst mayalso be of other metals such as steel, cobalt, eto., althoughexparimental tests indicate a decided advantage in favor of nickel overthe several other materials tested. In other words, according to onedefinition the catalyst may comprise, contain, or consist of a metal ormetals of the ferrous group.

Suitable pyrometer connections are provided at 9, 10, and 11. Thehydrocarbon gas, air, and steam supply lines are shown at 12, 13, and 14respectively, with respective control valves 15, 16 and 17. Thehydrocarbon gas, air, and steam as required by the particular operatingschedule pass thru the annular space 18 of the heat exchanger 19, thruconnecting line 20 and thence to the base of the reformer, thence thruthe .catalytic mass 6 where the reforming takes place in the presence ofthe catalytic mass. The resulting hot reformed gases pass from thereformer through off-take 22 to inner space 23 of the heat exchanger toconnecting pipe 24 provided with stack valve 24a to dip pipe 25 and thruwater seal 26 to outlet 27 and thence to mixing system thru valve 28 or29 depending upon cycle of operation as hereinafter described in Figures2, 3, and 4.

To start up the gas reformer or the gas reforming apparatus, as the gasreforming system as a whole may be referred to, hydrocarbon gases arefed through conduit 12 thru heat exchanger 18 to conduit 20 into bottomof the reforming chamber 1. Air is simultaneously admitted thru conduit20b thru valve 200 to bottom of the reformer, in such proportion as toproduce nearly complete combustion when the mixture of air andhydrocarbon gas is ignited, as by torch flame inserted thru port 811.The resulting combustion quickly brings the reforming chamber to therequired temperature. The combustion products are conducted from thereformer thru the heat exchanger 23 and allowed to escape thru therelief or stack valve 24a to the atmosphere. When the desiredtemperature of the reforming chamber is attained, as for example 1300F., and which temperature for certain gases and conditions is a normaltemperature,then the air supply from 20b is discontinued, by closingvalves 20c and 24a; and the first step of the reforming cycle isstarted. Hydrocarbon gases at the proper rate continue to flow thru thereformer wherein, in the presence of the catalyst, decomposition orreaction takes place. The products of this decomposition or reaction arefree carbon and lighter fixed gases. Substantially all of the freecarbon produced is retained on the surface of the catalyst. The gasesresulting from said decomposition pass from the reformer thru heatexchanger 23 (thus preheating the incoming hydrocarbon gases) to conduit24 and thru the water seal 26 and are subsequently recovered in themixing system hereinafter described. When the temperature of thereformer lowers to the predetermined point, the operation of this Step(1) is terminated by closing valve 15. The reformer is now ready foroperation of Step (2) as heretofore described. Valve 16 is opened andair is passed under suitable pressure thru the heat exchanger space 18to conduit 20 into the bottom of the reformer chamber and in contactwith the hot carbon deposited on the catalyst during Step 1. The oxygenfrom the air thus injected converts part of the deposited carbon toproducer gas and at the same time raises the temperature of thereforming chamber due to the exothermic nature of the producer gasreaction. The resulting gas produced during this step is conducted thruthe heat exchanger space 23 to seal 26 in the same manner as abovedescribed in Step 1) and subsequently recovered in the mixing meanshereinafter described. When the proper predetermined temperature of thereforming chamber is reached the operation of Step 2 is terminated byclosing valve 16 and the reformer is ready for Step (3) as heretoforedescribed wherein valve 17 is opened and steam is passed into thereforming chamber in like manner as Steps (1) and .(2) thru heatexchanger space 18 where it is superheated before delivering to thereforming chamber by means of conduit 20. The superheated steam ispassed thru the reformer in contact with. the remainder of the hotcarbon on the surface of the catalyst whereby the steam is decomposed byreaction with the hot carbon, to water gas. The temperature of thereformer is lowered because of the endothermic nature of the reaction.The resulting water gas passes from the reformer thru heat exchangerspace 23, thus superheating the incoming steam, to seal 26 in the samemanner as above described in Steps (1) and (2) and subsequentlyrecovered in the mixing means hereinafter describedwhen the properpredetermined minimum temperature of the reforming chamber is attained,the operation of Step (3) is terminated by closing valve 17 thuscompleting the cycle.

By way of example when the gas reformer is in normal operation thetemperature within the reforming chamber is above 1000 F., varyingthruout the cycle in accordance with the various endothermic andexothermic reactions which occur within the reforming chamber during thecycle. The variations in temperature are limited by the thermal capacityof the reforming chamber contents (catalytic mass, and any inertmaterial such as refractory checker brick which may have been insertedfor the purpose of increasing the thermal capacity).

The hydrocarbon gases, steam and air flowing to the reformer, arepreheated by the gases leaving the reformer by means of heat exchangersas-' sociated with the off-take piping and water seal.

SYSTEMS on PLANTS or FIGURES 2, 3, AND 4 Each of the systems of Figures2, 3 and 4 employs a gas reforming process such as fully described inconnection with Figure 1, and the gas reformer R of each of the Figures2, 3 and 4 is the same in essentials of construction, function, and modeof operation as the gas reformer shown and fully described in connectionwith Figure 1.

a System Figure 2 This Figure 2 illustrates diagrammatically a systemwhereby hydrocarbon gases, air, and steam, are supplied thru lines 12,13 and 14 respectively to the reformer R and treated or reformed in amanner previously described in respect to Figure 1, and the resultingreformed gases produced from the complete reforming cycle are conductedthru line 27-having bleed valve 29 normally closed.-thru valve 28 andline 30 to a storage holder 31 wherein the gases are thoroughly mixed bydiffusion. The three steps are so proportioned in regard totemperatures, and thruput and duration of each stage that the combinedgases constituting the resulting mixed gases approximate thepredetermined specifications. However, to exactly meet the predeterminedspecifications part of the gas made during Step 2 and/or Step 3 ispurged to the atmosphere by means of valve 29.

System of Figure 3 This Figure 3 illustrates diagrammatically areforming system whereby hydrocarbon gases, air, and steam are suppliedthru lines 12, 13 and 14 respectively to reformer R and treated orreformed in a manner previously described in respect to Figure 1, andthe resulting gases from Step (1) and Step (3) are conducted thru line27 and valve 28 (valve on line 29 is closed) and thru line 30 to thestorage holder 31. The gas produced during the reforming Step (2) isconducted thru line 27 thru valve on line 29, (valve 28 is closed) tothe lean gas holder 32. The lean gas from holder 32 is conducted thruline 33 to a point MX at which point the lean gas is admitted to line 30and conducted to the storage holder. The flow of the lean gas thru line33 is automatically controlled by valve 34 to maintain a uniform B. t.u. per cu. ft. of the gas in the storage holder 31. Valve 34 is actuatedby any well known B. t. u. (heatin value) controller and which B. t. u.controller would receive a continuous sample of gas from the reformedgas holder and automatically varies the setting of valve 34 to maintaina constant heating value of the reformed gas in the storage holder forthe specific (finished) gases desired from any complete cycle ofoperation. In the event that there is a surplus of lean gas from anycycle of operation, such gas may be conducted thru line 35 to anydesired point, as for example, for use as fuel.

System of Figure 4 This Figure 4 illustrates diagrammatically areforming system whereby hydrocarbon gas, air, and steam, are suppliedthru lines 12, 13 and 14 respectively to reformer R and treated orreformed in a manner previously described in respect to Figure 1, andthe resulting gases from Step (1) and Step (3) are conducted thru line2''! and valve 28 (valve on line 29 is closed) and thru line 30 to pointMX on line 30, at which point the reformed gases mix with themanufactured gases produced from an existing gas plant, while flowing toand into the storage holder 31. The gas produced during the reformingStep (2) is conducted thru line 27 thru valve 29 (valve 28 is closed) tothe lean gas holder 32. The lean gas from holder 32 is thereafterconducted thru line 33 to a point MXi in line 30, at which point thelean gas is mixed in the proper proportions with the gases flowing toand into the storage holder 31. The flow of the lean gas thru line 33 to.point MXi is automatically controlled by valve 34 to maintain a uniformB. t. u. per cu. ft. of the gases in the storage holder 31. Valve 34 isactuated by any well known B. t. u. controller, and whichB. t. u.controller receives a continuous sample of the gas from the storageholder and by nature of its operation automatically varies the settingof valve 34 (electrically operated) to allow proper volume of lean gasto flow to point MX1 and thus maintain the desired quality of mixed gasin the storage holder. Any surplus of lean gas produced from any cycleof operation may be conreformer in suspension with the gases.

ducted thru line 35 to any desired point for use as fuel.

The three step process as above particularly described, and themodification thereof as also above outlined, can be carried out in thegas reformer-of Figure l and can also be employed in the various systemssuch as that shown in Figures 2, 3 and 4 which rely for theirperformance upon, and which include, gas reformer of Figure 1.

As previously indicated, the three step proc-' ess can be materiallymodified and the modification will still be in the broad aspects of theinvention. By way of further example, the following processes, namelythe two step per cycle process, and the continuous process wherein allthree steps are combined, are sufficiently described hereinafter.Moreover each of these processes can be readily performed in thereformer of Figure 1' and can also be employed in system of Figures 2, 3and 4.

Dmsorrrrron or rm: TWO-STEP Process The two step reformed gas processconsists of a decomposition step and an air blowing (producer gas) stepper cycle. In the decomposition Step (1) of the cycle, hydrocarbon gasesare fed into the reforming chamber (previously heated to the requiredtemperature) wherein they are decomposed or reacted upon preferably inthe presence of a catalyst containing nickel. The products of thedecomposition or reaction are (1) a gas, composed largely of hydrogen,methane, and undecomposed hydrocarbon gases, the resulting gases passout of the reformer and are subsequently recovered; and (2) free carbon,substantially all of which is retained on the surface of the catalyst,and which catalyst thus serves to mechanically filter the free carbon asproduced and prevent its passing out of the The reaction is endothermic,causing the reformer temperature to drop 50-300 F. below the initialtemperature of this step.

Upon completion of Step 1, the air blowing (producer gas) Step 2 iscommenced wherein air is passed into the reformer to serve twopurposes:--first, all of the carbon deposited in the catalyst duringStep (1) is converted to producer gas; and second as a consequence ofthe exothermic nature of the reaction the temperature of the reformer israised 50-300 F. above the initial temperature of this step. Theproducer gas formed passes out of the reformer and as desired part orall is subsequently recovered.

The two steps above described constitute a complete cycle; and thecycles are repeated. All of the gases produced and recovered during thedecomposition step are mixed with all or part of the gases producedduring the air blowing (producer gas) step; the resulting mixtureconstituting the reformed gases, and which resulting reformed gases havea specific gravity between the range of .65 to .70 as compared with air,and a heating value between the range of 500-1000 B. t. u. per cu. ft.

DESCRIPTION or rm: CONTINUOUS (SINGLE S'rnr) Pnocnss In the continuousreforming process, all three steps of the three step process abovedescribed are simultaneously carried out as follows:-

A mixture of hydrocarbon gases, air and steam,

in predetermined proportions, preferably preheated, are continuously fedinto a hot reformer having a temperature between the ranges of 1000-1600F., in contact with the hot catalytic mass. The proportion of air in themixture is sufficient only to cause partial combustion of thehydrocarbon gases and to maintain constant the desired temperature ofthe reformer. The heat generated by the partial combustion, and thepresence of the catalyst causes decomposition and reforming of thehydrocarbon gases and steam and the reaction is performed without theproduction of carbon residue. The resulting reformed gases as withdrawnfrom the reformer have a specific gravity between the range of .70-.80and a heating value between the range of 400-700 B. t. u. per cu. ft.depending upon the proportion of air, steam, and hydrocarbon gases inthe inflowing mixture.

In order to differentiate between the various processes as abovedescribed, namely the three step, two step, and the continuous (singlestep) process, the following data on the results obtained with eachprocess is given as compared with standard manufactured city gas:-

It is hereby pointed out that in any of the systems above described, itis possible to produce resulting finished gases, or a mixture of gaseswhich may be termed finished gases that satisfy the requirements ofstandard manufactured city gases, and which can be used as a substitutefor, or interchangeably with, varying grades of standard manufacturedcity gases and which finished gases are what may be referred to ascombustible fixed gases.

The improvements herein set forth are not limited to the preciseconstruction and arrangement shown and described for it will beappreciated that they may be realized in various forms, ways andmodifications without departing from the spirit and scope of theinvention.

What is claimed is:-

1. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which includes three distinct steps per cycle, whereinaccording to Step (1) hydrocarbon gases are introduced into a reformingchamber, in contact with a hot catalytic mass containing nickel, and/oriron, and any carbon remaining which has been deposited as a result ofthe thermal decomposition of the hydrocarbon gases in the presence ofsaid nickel and/or iron, having a temperature between the range of1000-1600 F., decomposing the hydrocarbon gases in the presence of thecatalytic mass, into reformed gases and free carbon, retaining said freecarbon in the reforming chamber, wherein according to Step (2) air isintroduced into the reformer in contact with the hot carbon, and in thepresence of the catalyst, thus converting a portion of said carbon intoproducer gas; and wherein according to Step (3) steam is introduced intothe reforming chamber in contact with the remainder of the hot carbon,thus converting the carbon by reaction with the steam into water gas;said method also includes withdrawing in consecutive order, theresulting hot gases as produced from each step in a manner whereby heatis imparted therefrom to the inflowing hydrocarbon gas, air and steamtreated during each step, to preheat the latter; mixing the resultinggases produced from each step to produce a mixture of gases havingproperties substantially the same as standard manufactured city gas.

2. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which includes three distinct steps per cycle, whereinaccording to Step (1) hydrocarbon gases are introduced into a reformingchamber, in contact with a hot catalytic mass having a temperaturewithin the range of 1000 to 1600 degrees F., and which said catalyticmass comprises a metal or metals of the ferrous group and any carbonwhich has been deposited as a result of the thermal decomposition of thehydrocarbon gases in the presence of the catalytic mass, decomposing thehydrocarbon gases in the presence of the catalytic mass into reformedgases and free carbon, retaining said free carbon on the surface of thecatalyst; wherein according to Step (2) air :is introduced into thereformer in contact with the hot carbon retained on the catalyst, thusconverting a portion of said carbon into producer gas; and whereinaccording to Step (3) steam is introduced into the reforming chamber incontact with the remainder of the hot carbon on the catalyst, thusconverting said remaining hot carbon by reaction with the steam intowater gas; said method also including withdrawing in consecutive order,the resulting hot gases as produced from each step in a manner wherebyheat is imparted therefrom to the infiowing hydrocarbon gases, air, andsteam treated during each step to preheat the latter.

3. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which consists of three distinct steps per cycle, whereinduring Step (1) hydrocarbon gases are introduced into a reformingchamber in contact with a hot catalytic mass having a temperature withinthe range of 1,000 to 1,600 degrees F., and which said catalytic masscontains a metal or metals of the ferrous group and any remaining carbonwhich has been deposited as a result of the thermal decomposition of thehydrocarbon gases in the presence of the catalytic mass, decomposing thehydrocarbon gases in the presence of the catalytic mass intoreformedgases and free carbon, retaining said free'carbon on the surface of thecatalyst; wherein during Step (2) air is introduced into the reformer incontact with the hot carbon retained on the catalyst, thus con.- vertinga portion of said carbon into producer gas; and wherein during Step (3)steam is introduced into the reforming chamber, in contact with theremaininghot carbon, thus converting the carbon by reaction with thesteam into water gas, and which cycle includes withdrawing inconsecutive order, the resulting hot gases as produced from each step ina manner whereby heat is imparted therefrom to the inflowing materialtreated during each step, to preheat the latter.

4. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which consists of three distinct steps per cycle, whereinduring Step (1) hydrocarbon gases are introduced into a reformingchamber in contact with a hot catalytic mass having a temperature withinthe range of 1,000 to 1,600 degrees F., and which said catalytic masscontains a metal or metals of the ferrous group and any remaining carbonwhich has been deposited as a result of the thermal decomposition of thehydrocarbon gases in the presence of the catalytic mass, decomposing thehydrocarbon gases in the presence of the catalytic mass into reformedgases and free carbon, retaining free carbon on the surface of thecatalyst; wherein during Step (2) air is introduced into the reformer incontact with the hot carbon, thus converting a portion of said carboninto producer gas; and wherein during Step (3) steam is introduced intothe reforming chamber in contact with the hot carbon, thus convertingsaid remaining hot carbon by reaction with the steam, into water gas,and which cycle includes the withdrawing in consecutive order, theresulting hot gases as produced from each step.

5. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which comprises three distinct steps per cycle of successivecycles wherein according to the first step of each cycle hydrocarbongases and air are introduced simultaneously in predeterminedproportions, into a reforming chamber, in contact with a hot catalyticmass at a temperature within the range of 1,000 to 1,600 degrees F., andwhich said catalytic mass comprises a metal or metals of the ferrousgroup and any remaining carbon which has been deposited as a result ofthe thermal decomposition of the hydrocarbon gases in the presence ofthe catalytic mass, decomposing or reacting the hydrocarbon gases in thepresence of the catalyst into reformed gases andfree carbon, retainingsaid free carbon on the surface of the catalyst; wherein according tothe second step, air is introduced into the reformer in contact with thehot carbon retained on the surface of the catalyst, thus converting aportion of said carbon into producer gas; and wherein according to thethird step, steam is introduced into the reforming chamber in contactwith the remaining hot carbon on the catalyst, thus converting the saidremaining hot carbon by reaction with the steam, into water gas, whichmethod also comprises withdrawing in consecutive order during eachcycle, the resulting hot gases as produced in the particular stepwhereby heat is imparted from the hot outfiowing gases to the infiowingmaterial treated during this particular step, to preheat the latter.

6. The manufacture from hydrocarbon gases of a combustible fixed gas bythe method which comprises successive cycles in which there are threedistinct steps per cycle and wherein during step one of the cycle,hydrocarbon gases and steam are introduced simultaneously inpredetermined proportions, into a. reforming chamber in contact with ahot catalytic mass at a temperature within the range of 1000 to 1600degrees F., and which said catalytic mass comprises a metal or metals ofthe ferrous group and any remaining carbon which has been deposited as aresult of the thermal decomposition of the hydrocarbon gases in thepresence of the catalytic mass, decomposing or reacting the hydrocarbongases and steam in the presence of the hot catalyst into reformed gasesand free carbon and retaining free carbon in the presence of thecatalyst; wherein during step two air is introduced into the reformer incontact with the hot carbon, thus converting a portion of said carboninto producer gas; and wherein during step three, steam is introducedinto the reforming chamber in contact with the remainder of the hotcarbon; thus converting the remaining hot carbon by reaction with thesteam into water gas; withdrawing in consecutive order the resulting hotgases produced from each step in a manner whereby heat is impartedtherefrom to the infiowing material treated during each step of eachsuccessive cycle, to preheat the latter.

7. The manufacture from hydrocarbon gases'of a combustible fixed gas bythe method which comprises successive cycles in which there are threedistinct steps per cycle and wherein during Step one of the cycle,hydrocarbon gases and steam are introduced simultaneously inpredetermined proportions, into a reforming chamber in contact with ahot catalytic mass at a temperature within the range of 1000 to 1600degrees F., and which said catalytic mass comprises a metal or metals ofthe ferrous group and any remaining carbon which has been deposited as aresult of the thermal decomposition of the hydrocarbon gases in thepresence of the catalytic mass, decomposing or reacting the hydrocarbongases and steam in the presence of the hot catalyst into reformed gasesand free carbon and retaining free carbon in the presence of thecatalyst; wherein during Step two, air is introduced into the reformerin contact with the hot carbon, thus converting a portion of said carboninto producer gas; and wherein during Step three, steam is introducedinto the reforming chamber in contact with the hot carbon; thusconverting hot carbon by reaction with the steam into water gas;withdrawing in consecutive order, the resulting hot gases as producedfrom each step.

8. The manufacture from hydrocarbon gases of a reformed combustiblefixed gas by the method which includes two distinct steps per cycle,wherein according to Step (1) hydrocarbon gases are introduced into areforming chamber, in contact with a hot catalytic mass having atemperature within the range of 1000 to 1600 degrees F., and which saidcatalytic mass comprises a metal or metals of the ferrous group and anyremaining carbon which has been deposited as a result of the thermaldecomposition of the hydrocarbon gases in the presence of the catalyticmass, decomposing or reacting the hydrocarbon gases in the presence ofthe catalytic mass into reformed gases and free carbon, retaining freecarbon in the presence of the catalyst; and wherein according to Step (2air is introduced into the reformer in contact with the hot carbon, thusconverting said carbon into producer gas; said method also includeswithdrawing in consecutive order, the resulting hot gases as producedfrom each step in a manner whereby heat is imparted therefrom to theinflowing hydrocarbon gases,

and air, treated during each step, to preheat the latter.

9. The manufacture from hydrocarbon gases of a reformed combustiblefixed gas by the method which includes two distinct steps per cycle,wherein according to Step (1) hydrocarbon gases are introduced into areforming chamber, in contact with a hot catalytic mass having atemperature within the range of 1000 to 1600 degrees F., and which saidcatalytic mass comprises a metal or metals of the ferrous group and anyremaining carbon which has been deposited as a result of thedecomposition of the hydrocarbon gases in the presence of the catalyticmass, decomposing or reacting the hydrocarbon gases in the presence ofthe catalytic mass into reformed gases and free carbon, retaining saidfree carbon on the surface of thecatalyst; and wherein according to Step(2) air is introduced into the reformer in contact with the hot carbonretained on the catalyst, thus converting all of the said carbon intoproducer gas; said method also includes withdrawing in consecutiveorder, the resulting hot gases as produced from each step.

10. The manufacture from hydrocarbon gases of a reformed combustible-gasby the method which consists of continuously introducing a mixture ofhydrocarbon gases, air, and steam in predetermined proportions,preferably preheated, into a reforming chamber, in contact with a hotcatalytic mass that comprises a metal or metals of the ferrous group andany remaining carbon which has been deposited as a result of the thermaldecomposition of the hydrocarbon gases in the presence of the catalyticmass, at a temperature between the ranges of 1000-1600" F., theproportion of air suflicient only to cause partial combustion of thehydrocarbon gases and maintain a constant temperature of the reformingchamber; decomposing and reforming the hydrocarbon gases andsteam in thepresence of the catalyst, by the heat generated by said partialcombustion; thus continuously producing without the formation of carbonresidue, a reformed combustible fixed gas of lower calorific value perunit of volume and a larger volume than the hydrocarbon gases from whichit was produced; and continuously withdrawing the resulting gases fromthe reformer, said resulting gases having a specific gravity between therange of .70.80, and a heating value between the range of 400-700 B. t.u. per cubic foot.

GEORGE ALAN DAVIS.

